Aminodicyano alkene compounds

ABSTRACT

WHEREIN EACH Rii is an alkyl radical and Riii is selected from the group consisting of alkylene and oxydialkylene radicals. Also described are (1) a process for preparing the novel compounds of this invention which comprises reacting a secondary amine and a dicyano-substituted conjugated diene, and (2) a process for preparing the trans isomer of the novel compounds of this invention which comprises reacting a secondary amine and a dicyano-substituted conjugated diene in the presence of an aliphatic monocarboxylic acid. The compounds of this invention are useful as bactericides.   HAVING FROM 8 TO 26 CARBON ATOMS PER MOLECULE, WHEREIN EACH R is individually selected from the group consisting of hydrogen, alkyl and cycloalkyl; each Ri is individually selected from the group consisting of R and aryl and Q is selected from the group consisting of   Described herein are novel aminodicyano alkenes of the formula

United States Patent [191 Vives AMINODICYANO ALKENE COMPOUNDS [75]Inventor: Van C. Vives, Bartlesville, Okla.

[73] Assignee: Phillips Petroleum Company,

Bartlesville, Okla.

22} Filed: Apr. 11, 1974 [211 Appl. No: 460,044

[52] 13.8. CI 260/247; 260/239 B; 260/293.51; 260/293.75; 260/326.62;260/465 E; 260/4655 R; 260/465.8 R; 424/244; 424/248; 424/267; 424/274;424/304 [51] Int. Cl. ..C07C 121/45; CO7D 211/34; CO7D 295/14 [58] FieldOf Search 260/247, 465 E, 465.5 R, 260/293.51, 293.75, 239 B, 326.62

{56] References Cited UNITED STATES PATENTS 2,444,882 7/1948 Tawney260/465.8 R 2,527,510 10/1950 Allen et al. 260/4655 R 3,138,631 6/1964Frazza et a1 260/465 E Primary ExaminerAnton H. Sutto AssistantExaminerMichael Shippen [57] ABSTRACT Described herein are novelaminodicyano alkenes of the formula Dec. 9, 1975 having from 8 to 26carbon atoms per molecule, wherein each R is individually selected fromthe group consisting of hydrogen, alkyl and cycloalkyl; each R isindividually selected from the group consisting of R and aryl and Q isselected from the group consisting of 20 Claims, N0 DrawingsAMINODICYANO ALKENE COMPOUNDS This invention relates to aminodicyanoalkene compounds.

Heretofore, aminodicyano alkene compounds of the formula having from 8to 26 carbon atoms per molecule, wherein R is hydrogen, alkyl orcycloalkyl, R is R or aryl, and Q is R" rr R iN CNR containing from 8 to26 carbon atoms per molecule, wherein each R is individually selectedfrom the group consisting of hydrogen, alk yl having from l to 4 carbonatoms and cycloalkyl having from 3 to 6 carbon atoms; each R isindividually selected from the group consisting of R and aryl havingfrom 6 to l carbon atoms; and Q is selected from the group consisting ofwherein each R is individually selected from the group consisting ofalkyl having from 1 to 10 carbon atoms and R is selected from the groupconsisting of alkylene and oxydialkylene having from 4 to 6 carbonatoms.

In one embodiment of this invention there is provide a process for thepreparation of novel aminodicyano compounds of the formula Jill. l l

as hereinbefore described, which comprises reacting a secondaryarninehaving the formula in H 0 wherein Q is as described above, with adicyano-substituted conjugated diene according to the following generalreaction equation wherein R and R are as described above.

In another embodiment of this invention there is provided a process forthe preparation of the trans isomer of the novel aminodicyano alkenecompounds of this invention, which comprises conducting the abovereaction for the preparation of (l) in the presence of an aliphaticmonocarboxylic acid having from I to 4 carbon atoms per molecule.

Representative compounds described by formula (I) include:l-piperidino-2,3-dicyano-2-butene, l-pyrrolidino-2,3-dicyano-2-butene,l-dimethylamino-2,3- dicyano-2-butene, l-di-n-octylamino-2 ,3-dicyano-2- butene, l-morpholin o-2,3-dicyano-2-butene, 2-piperidino-3,4-dicyano-3-hexene, 2-morpholino-3,4- dicyano-3-pentene,5-dimethylamino-6,7-dicyano-6- dodecene, l-p-tolyll-pyrrolidino-2,3-dicyano-2- butene, l -pheny1- l-di-n-butylamino-2,3-dicyano-2- butene, l-cyclopro pyll-piperidino-2,3-dicyano-2- butene, l-cyclohexyll -morpholino-2,3'dicyano-2-butene, l -alpha-naphth yll -pyrro1idino-2,3-dicyano-2- butene,2-dimethylamino-3,4-dicyano-3-octene,S-din-butylamino-6,7-dicyano-o-dodecene, 2,l l-dimethyl-5-diethylamino-6,7-dicy ano--dodecene,l-di-ndecylamino-2,3-dicyano-2-butene and the like.

Representative compounds described by formula (II) include:dimethylamine, diethylamine, dibutylamine, di-n-octylamine,didecylamine, pyrrolidine, piperidine, morpholine and the like.

Representative compounds described by formula (ill) include:l,3-butadiene-2,3-dicarbonitrile; 2,4-hexadiene-3,4-dicarbonitrile;2,4-pentadiene-3,4-dicarbonitrile', 5,7-dodecadiene6,7-dicarbonitrile;l-ptolyl-1,3-butadiene-2,3-dicarbonitrile; l-phenyl-l ,3-butadiene-2,3dicarbonitrile; 5,8-di-n-butyl-5,7-dodecadiene-6,7-dicarbonitrile; 2,7-dimethyl-3,6-diphenyl-3,S-octadiene-4,5-dicarbonitrile; l-cyclopropyl-l,3-butadiene-2,3-dicarbonitrile; l-cyclohexyll ,3- butadiene-Z,3-dicarbonitrile', l'alpha-naphthyl-l ,3- butadiene-2,3dicarbonitrile;2,4-octadiene-3,4-dicarbonitrile, and the like.

in a presently preferred embodiment, the dicyanosubstituted cnnjugateddiene of formula (Ill) is l,3- butadiene-2,3-dicarbonitrile, which, onamination with a suitable secondary amine, gives the l-amino-2-butenederivative.

l,3-Butadiene-2,3dicarbonitriles can be obtained by the known thermalisomerization of a cyclobutene-l ,2- dicarbonitrile, which is preparedfrom a cyclobutanel ,2-dicarbonitrile.

Representative monocarboxylic acids which can be used in the process ofthis invention include formic acid, acetic acid, propionic acid, butyricacid and isobutyric acid. In a presently preferred embodiment the acidis acetic acid.

The process of this invention is preferably conducted in the presence ofan inert diluent. Suitable diluents include polar and non-polar diluentswhich are inert to the reactants under reaction conditions, includingbut not limited to acyclic and cyclic aliphatic ethers. aliphaticnitriles. aromatic hydrocarbons. halogenated aromatic and aliphatichydrocarbons and the like. Representative diluents include benzene.toluene. tetrahydrofuran, diethyl ether, chlorobenzene. chloroform,methylene chloride. carbon tetrachloride. acetonitrile and the like.Ethereal diluents can be used without spe cial purification; however. itmay be advantageous to remove any peroxidic residues from such diluentsprior to contacting such diluent with the dicarbonitrile feedstock. Suchperoxidic residues can initiate polymeriza tion of such feedstock. Theperoxidic residues can be removed by distilling the ether from a slurrywith lithium aluminum hydride.

The molar ratio of secondary amine to diene can be in the range of 5:1to 1:5, preferably 3:1 to 1:3. Very large excesses of either reactantshould be avoided to minimize side products which can complicateisolation and recovery of the product.

In the process for the preparation of the trans isomer of theaminodicyano alkene compounds of this inven tion, the molar ratio ofmonocarboxylic acid to secondary amine can range from 0.1:] to :1,preferably from 0.511 to 2:1.

The reaction is carried out at a temperature in the range of 50 to 150C.. preferably from 0 to about 100 C.

The reaction is normally conducted under atmospheric pressure. althougha pressure in the range of 0 to 100 psig can be used.

Reaction time will vary. inter alia. according to the reactants,reaction temperature. relative reactant concentrations and the like. Ingeneral. reaction time will be between 0.1 and 24 hours.

The reaction can be conducted in any suitable apparatus. An inertreaction atmosphere can be used if desired. The reaction can beconducted batchwise or as a continuous process.

The novel aminodicyano alkene compounds of this invention can beseparated from the reaction mixture by methods known in the art, such asby precipitation, extraction, fractional crystallization, fractionaldistillation and the like.

The compounds of this invention are useful as bactericides. Applicationof the compounds of this invention for the purpose disclosed can be madefrom solutions in suitable solvent carriers or in combination withsupplementary agents, adjuvants, other control agents and the like. Theyare employed in a bactericidal amount, generally from about 0.01 toabout 90 weight percent of the tea] composition.

The following examples illustrate the invention:

EXAMPLE I A mixture of 0.4659 g (0.0045 mol) of1,3-butadiene-2,3-dicarbonitrile and 50 ml of tetrahydrofuran wascharged to a 100 ml 3-neck round-bottom flask equipped with magneticstirrer and fitted with a cold finger condenser, thermometer and rubberseptum. The condenser was cooled with dry ice. The system was maintainedunder a nitrogen atmosphere. 130 ml (0.0054 mol) of gaseousdimethylamine were injected below the surface of the stirred solution.The reaction mixture was stirred at room temperature for about 3.5hours.

The reaction mixture was concentrated on a rotary evaporator. giving0.64 g of a dark brown liquid resi due. Vacuum sublimation of the liquidresidue at about 55-65 C. and 2 mm pressure gave 0.3423 g of ahygroscopic white low melting solid. Recrystallization of the solid fromdichloromethane/hexane gave two crops of white crystals having acombined weight of0. 1267 g. The first crop of crystals had a meltingpoint of 34.535.5 C. The two crops of crystals were combined forelemental analysis:

Calculated for C H N C. 64.4; H, 7.43; N, 28.17. Found: C, 64.4; H, 7.4;N. 28.3.

Mass and nuclear magnetic resonance spectral data indicated that theproduct was l-dimethylamino-2.3- dicyano-Z-butene.

EXAMPLE ll To a stirred mixture of 2.19 g (0.02 mol)1,3-butadiene-2,3-dicarbonitrile in ml tetrahydrofuran was added 1.74 g(0.02 mol) of morpholine at room temperature. After 1.5 hours themixture had taken on a dark blue color.

After standing overnight the dark blue reaction mixture was treated withcharcoal and filtered. The filtrate was concentrated on a rotaryevaporator giving 3.6 g of a brown residue. This residue was extractedseveral times with hexane and the hexane extracts were combined andtreated with charcoal. After filtration to remove the charcoal, thehexane solution was cooled to 20 C. to give 1.88 g of fine whitecrystals having a melting point of 7983 C. which gave the followingelemental analysis:

Calculated for C l-l N O:% C, 62.87; H, 6.76; N. 22.00. Found: C. 63.22:H.674: N. 22.40.

Mass and nuclear magnetic resonance spectral data indicated that theproduct was l-morpholino-2,3- dicyano-Z-butene.

EX AMPLE III A mixture of 1.47 g (0.0l4 mol) l,3-butadiene-2,3-dicarbonitrile and 50 ml benzene was charged to a 3- neck round-bottomflask fitted with water-cooled condenser. thermometer and a droppingfunnel containing 1.24 g (0.015 mol) piperidine in about 15 ml benzene.The solution in the reaction vessel was stirred and heated to reflux asthe piperidinebenzene solution was added dropwise over a period of 9minutes. The reaction mixture was heated an additional 32 minutes afterall the piperidine had been added.

The reaction mixture was cooled to room temperature, filtered, and thefiltrate was treated with charcoal before most of the benzene solventwas evaporated under a stream of nitrogen to give a black viscous oil.Through the use of silica gel column chromatography two major componentswere recovered to give 1.89 g of cisand transisomers oflpiperidino-2,3-dicyano-2- butene. The trans-isomer (m.p. 6869 C.)eluted first from the silica gel chromatography column and was purifiedby rcrystallization from a mixture of ether and hexane. The transisomerwas eluted from the column with a 30/70 volume mixture of ether/hexane.The cisisomer (mp 48-49 C.) was eluted from the column with ether andwas purified by recrystallization from a mixture of ether and hexane.The structural assignment of cisand transwas made on the basis ofnuclear magnetic resonance spectral data.

EXAMPLE IV A sample of lpiperidino-Z.3-dicyano-2butene was tested foruse as a bactericide. The sample, containing a mixture of cisandtrans-isomers, was incorporated into an agar nutrient medium to producea concentration of 32 ppm. The resulting plates were innoculated witheach of Escherichia coli, Haemophilus gallinarum and Staphylococcusaureus bacteria and incubated for 48 hours. Growth inhibition was ratedby visual comparison with growth on untreated agar. No growth of theorganisms was apparent.

This example illustrates the effectiveness oflpipcridino-2,3-dicyano-2-butene as a bactericide.

EXAMPLE V A mixture of 3.15 g (0.037 mol) of piperidine, 2.5 ml (0.043mol) of glacial acetic acid and 75 ml of benzene was charged to a 3-neckround-bottom flask fitted with water-cooled condenser, thermometer,dropping funnel and magnetic stirrer. The solution in the reactionvessel was stirred and heated to refiux. A solution of 1.86 g (0.018mol) of 1,3-butadiene-2,3-dicarbonitrile in about 50 ml of benzene wasadded dropwise to the stirred reaction mixture over a period of about 17minutes. When addition was complete, the reaction mixture was stirred atreflux for an additional 33 minutes.

The reaction mixture was cooled to room temperature and the benzene wasremoved under vacuum leaving a dark brown residue. This residue wasextracted with hexane. The hexane extract was concentrated, then cooledto 20 C. to give 2.92 g of off-white crystals. An additional 0.23 g ofsuch crystals was obtained from the mother liquor. The crystals werecombined, then recrystallized from hexane to give 2.13 g oftranslpiperidino-Z,3-dicyano-2-butene, having a melting point of 6768.2C. The trans-structure was assigned on the basis of melting point andnuclear magnetic resonance spectral data.

this example illustrates the stereospecific reaction of a secondaryamine and a dicyano-substituted conjugated diene.

EXAMPLE VI A mixture'of 1.47 g 0.014 mol) of 1,3-butadiene-2,3-dicarbonitrile and 50 ml of benzene was charged to a 3-neckround-bottom flask equipped with a watercooled condenser, thermometer,dropping funnel and magnetic stirrer. The solution was heated to reflux,with stirring. A solution of 3.4 g (0.014 mol) of di-noctylamine inbenzene was added, dropwise over a period of 30 minutes. to the reactionvessel.

The reaction mixture was cooled to room temperature, then concentratedon a rotary evaporator, giving a greenish-black residue. This residuewas extracted with hexane. The hexane extract was treated with charcoal,filtered, and concentrated to give 4.57 g of a greenish-black oil.Through the use of silica gel column chromatography, two compounds wereseparated from the oil. Component I was a bright yellow oil whichweighed 0.36 g. Component 1] weighed 0.32 g. Infrared and nuclearmagnetic resonance spectral data indicated that components I and 11 werethe cisand transisomers of ldi-n-octylamino-2,3-dicyano-2-butene.

EXAMPLE VII A 1.4 g (0.02 mol) sample of freshly distilled pyrrolidinewas added at room temperature to a stirred solution of 1.97 g (0.019mol) l,3-butadiene-2,3-dicarbonitrile in 75 m1 tetrahydrofuran. At theend of 1.5 hours, the mixture was concentrated under reduced pressure togive 3.36 g of a dark greenish-brown oil.

This oil was extracted with hexane and the hexane extract was treatedwith charcoal. After filtration to remove charcoal, the hexane extractwas concentrated to give 2.21 g of yellow oil. This yellow oil wasresolved to give a major component and a minor component. Infraredspectral data indicated that the components were the cisand transisomersof l-pyrrolidino-2,3- dicyano-Z-butene.

Reasonable variations and modifications of this invention will beapparent to those skilled in the art in view of this disclosure. Suchvariations and modifications are within the scope and spirit of thedisclosure.

1 claim:

1. An aminodicyano alkene of the formula o-ijd=d it having from 8 to 26carbon atoms per molecule, wherein each R is individually selected fromthe group consisting of hydrogen, alkyl having from 1 to 4 carbon atomsand cycloalkyl having from 3 to 6 carbon atoms, each R is individuallyselected from the group consisting of R and aryl having from 6 to 10carbon atoms, and Q is selected from the group consisting of and Clwherein each R is individually selected from the group consisting ofalkyl radicals having from 1 to 10 carbon atoms and R is selected fromthe group consisting of alkylene and oxydialkylene radicals having from4 to 6 carbon atoms.

2. The compound of claim 1 wherein each R is H, each R is H and Q isdimethylamino.

3. The compound of claim 1 wherein each R is H, each R is H and Q ismorpholino.

4. The compound of claim 1 wherein each R is H, each R is H and Q ispiperidino.

5. The compound of claim 1 wherein each R is H, each R is H and Q isdi-n-octylamino.

6. The compound of claim 1 wherein each R is H, each R is H and Q ispyrrolidino.

7. A process for the preparation of an aminodicyano alkene compound ofthe formula having from 8 to 26 carbon atoms per molecule, wherein eachR is individually selected from the group consisting of hydrogen, alkylhaving from 1 to 4 carbon atoms and cycloalkyl having from 3 to 6 carbonatoms; each R is individually selected from the group consisting of Rand aryl having from 6 to 10 carbon atoms; and Q is selected from thegroup consisting of wherein each R is individually selected from thegroup consisting of alkyl having from l to 10 carbon atoms and R" isselected from the group consisting of alkylene and oxydialkyleneradicals having from 4 to 6 carbon atoms, which comprises reacting asecondary amine having the formula l-l Q, wherein Q is as defined abovewith a dicyano-substituted conjugated diene having the formula wherein Rand R are as defined above, wherein said reaction is conducted at atemperature in the range of -50 to 150C and wherein the molar ratio ofsaid amine to said diene is in the range of :1 to I15.

8. The process of claim 7 wherein said reaction is conducted at atemperature in the range of 0 to about 100C.

9. The process of claim 7 wherein the molar ratio of said amine to saiddiene is in the range of 3:1 to 1:3.

10. The process of claim 7 wherein said conjugated diene is1,3-butadiene-2,3-dicarbonitrile.

11. The process of claim 10 wherein said amine is dimethylamine.

12. The process of claim 10 wherein said amine is morpholine.

13. The process of claim 10 wherein said amine is piperidine.

14. The process of claim 10 wherein said amine is din-octylamine.

15. The process of claim 10 wherein said amine is pyrrolidine.

16. A process for the preparation of the trans-isomer of an aminodicyanoalkene compound of the formula R" -N and n"' wherein each R isindividually selected from the group consisting of alkyl having from ito 10 carbon atoms and R is selected from the group consisting ofalkylene and oxydialkylene radicals having from 4 to 6 carbon atomswhich comprises reacting a secondary amine having the formula iN iN gwherein R and R are as defined above, in the presence of an aliphaticmonocarboxylic acid having from 1 to 4 carbon atoms per molecule,wherein said reaction is conducted at a temperature in the range of 50to l50C and wherein the molar ratio of said amine to said diene is inthe range of 5:1 to 1:5 and the molar ratio of said acid to said amineis in the range of 0.111 to 10:1.

17. The process of claim 16 wherein said reaction is conducted at atemperature in the range of 0 to about C.

18. The process of claim 16 wherein the molar ratio of said amine tosaid diene is in the range of 3:1 to l :3.

19. The process of claim 16 wherein said conjugated diene isl,3-butadiene-2,3-dicarbonitrile, said amine is piperidine and said acidis acetic acid.

20. The process of claim 16 wherein the molar ratio of said acid to saidamine is in the range of0.5:l to 2:1.

1. AN AMINODICYANO ALKENE OF THE FORMULA
 2. The compound of claim 1wherein each R is H, each Ri is H and Q is dimethylamino.
 3. Thecompound of claim 1 wherein each R is H, each Ri is H and Q ismorpholino.
 4. The compound of claim 1 wherein each R is H, each Ri is Hand Q is piperidino.
 5. The compound of claim 1 wherein each R is H,each Ri is H and Q is di-n-octylamino.
 6. The compound of claim 1wherein each R is H, each Ri is H and Q is pyrrolidino.
 7. A process forthe preparation of an aminodicyano alkene compound of the formula
 8. Theprocess of claim 7 wherein said reaction is conducted at a temperaturein the range of 0* to about 100*C.
 9. The process of claim 7 wherein themolar ratio of said amine to said diene is in the range of 3:1 to 1:3.10. The process of claim 7 wherein said conjugated diene is1,3-butadiene-2,3-dicarbonitrile.
 11. The process of claim 10 whereinsaid amine is dimethylamine.
 12. The process of claim 10 wherein saidamine is morpholine.
 13. The process of claim 10 wherein said amine ispiperidine.
 14. The process of claim 10 wherein said amine isdi-n-octylamine.
 15. The process of claim 10 wherein said amine ispyrrolidine.
 16. A process for the preparation of the trans-isomer of anaminodicyano alkene compound of the formula
 17. The process of claim 16wherein said reaction is conducted at a temperature in the range of 0*to about 100*C.
 18. The process of claim 16 wherein the molar ratio ofsaid amine to said diene is in the range of 3:1 to 1:3.
 19. The processof claim 16 wherein said conjugated diene is 1,3-butadiene-2,3-dicarbonitrile, said amine is piperidine and said acidis acetic acid.
 20. The process of claim 16 wherein the molar ratio ofsaid acid to said amine is in the range of 0.5:1 to 2:1.